Organic compound of quinquevalent phosphorus



Patented Aug. 26, 1941 UNITED STATES PATENT OFFICE ORGANIC COMPOUND OIQUINQUEVALIN'I' PHOSPHOBUS Philip Greeley Stevens, Montreal, Quebec,Callada, and Howard Sinclair Turner, SwarthnorePa.,aasisnorsto8.l.dnlontdeliemoah&

m, Delaware Del, a corporation oi No Drawing. Application Jane 5, 1939.Serial No. 277,562

29 Claims. (Cl. 260-400) tain a carbon-phosphorus bond. A still furtherobject is the preparation of tertiary alpha-hydroxyphosphonates whichhave the property of modifying surface tension. A still further objectis the preparation of novel derivatives of tertiaryalpha-hydroxyphosphonic acids which imparts unexpected properties tolubricating oils;

Other objectswill appear hereinafter.

These objects are accomplished by the following invention whichcomprises reacting a bromide or chloride of tervalent phosphorus, all ofthe valences of which are attached to other atoms by single bonds, witha ketone of at least ten-carbon atoms having on the carbonyl carbon atleast one open chain aliphatic radical, preferably of at least threecarbon atoms, preferably in the presence of a low molecular weightorganic monocarbox'ylic acid or anhydride thereof. In the case of thereaction with phosphorus trichloride or trlbromide, the resultingproduct is desirably hydrolysed with water or aqueous alkali. Theinvention also includes the products of the reaction, namely the dibasictertiary alpha-hydroxyphosphonic acids and their monoand diesters andsalts, the monobasic tertiary alpha-hydroxyphosphonic acids. salts, andesters thereof, and the phosphine oxide derivatives.

The tertiary alpha-hydroxyphosphonic acids of this invention areobtained by reacting a ketone of at least ten carbon atoms, in which atleast one completely open-chain aliphatic radical preferably of three ormore carbon atoms is attached to the carbonyl group, with phosphorustrichloride or tribromide in the presence of a low molecular weightcarboxylic acid or carboxylic acid anhydride. The tertiaryalpha-hydroxyphosphonic monobasic acids and phosphine oxide derivativesare obtained by the reaction of monoor dichlorophosphines or monoordibromophosphines on ketones of ten or more carbon atoms in which atleast one open-chain aliphatic radical preferably of three or morecarbon atoms is attached to the carbonyl group. The esters of tertiaryalpha-hydroxyphosphonic acids are obtained by reacting alcohols with theintermediate phosphonyl chlorides or bromides resulting from thereaction of phosphorus trlchloride or tribromide. or a dichlorophosphineor dibromophosphine on ketones of ten, or more carbon atoms in which atleast one completely openchain aliphatic radical preferably of three ormore carbon atoms is attached to the carbonyl group.

The invention is not to be restricted because of the followingtheoretical explanation. the probable mechanism oi the reaction betweenketones of ten or more carbon atoms, in which at least one open-chainaliphatic radical preferably of three or more carbon atoms is attachedto the carbonyl group, and phosphorus trichloride is the formation ofintermediate cyclic phosphonic acid chlorides which by the action ofalcohols or phenols are converted to esters. The proposed mechanism ofthe reaction may be illustrated as follows:

when an alcohol or phenol is used in place of water, esters are obtainedby the probable reaction:

If, in the reaction of the ketone, dimethoxychlorophosphine issubstituted for the phosphorus trichloride, the reaction mechanism isprobably as follows:

This is a very satisfactory method for making the neutral esters. v

If, in the reaction of the ketone, n-butyldi-, chlorophosphine(n-CaHaPCla) is substituted for the phosphorus trichloride, the reactionmechanism is probably as follows:

When alcohols or phenols are reacted with the cyclic phosphonic acidchloride, esters are formed.

wherein RCR contains at least ten carbon atoms, at least one of theorganic radicals R is an aliphatic radical, G is OH, OM, R, or OR, and Mishydrogen or a salt-forming atom or group. The preferred sub-class isthat of tertiary alpha-hydroxy dibasic phosphonic acids, 1. e.,derivatives of quinquevalent phosphorus wherein the phosphorus isattached to a carbinol, CO-I-I, group which is attached through carbonto two organic radicals, at least one of which is an open-chainaliphatic radical, two valences of the phosphorus are attached to oneoxygen and two valences are satisfied by hydroxyls, and the salts,preferably water-soluble, of these acids.

Other sub-classes are the esters of these dibasic acids, the monobasicacids, wherein one hydroxyl of the dibasic acids is replaced by anorganic radical attached to the phosphorus by a C-P linkage, e. g., anaryl or alkyl radical, the esters and salts of the monobasic acids, andthe phosphine oxide derivatives, wherein both ,hydroxyls of the dibasicacids are replaced by organic radicals, e. g., alkyl or aryl, attachedto the phosphorus by C--P linkages.

The more detailed practice of the invention is illustrated by thefollowing examples, wherein parts given are by weight. There are ofcourse many forms of the invention other than these specificembodiments.

, EXAMPLE I Disodium 8-hydroxy-8-pentadecanephosphonate A mixture of 118parts of pentadecanone-8, 156 parts of phosphorus trichloride, and 90parts of glacial acetic acid are placed in a reaction vessel closed witha calcium chloride vent and allowed to stand for 2 days. The reactionmixture is then evacuated to mm. and held at 70 C. for 2 hours. Theresidue is treated with 3000 parts of water and evaporated to dryness.The yield of free phosphonic acid amounts to 178 parts by weight. Thesodium salt is prepared by dissolving the free acid in dilute ethanoland neutralizing with a dilute aqueous sodium hydroxide solution. Watersolutions of disodium 8- hydroxy-8-pentadecanephosphonate foam readily;The sodium salt is an effective agent for promoting the wetting ofcotton textiles and also displays mold inhibiting action.

Exnmu II Disodium 12m nimum-12-tricosanephosphonate Suificient ether isadded to a mixture of 338 parts of tricosanone-lZ, 207 parts ofphosphorus trichloride, and 180 parts of glacial acetic acid to form ahomogeneous solution. The reaction mixture is allowed to stand at roomtemperature for one week and then subjected to a vacuum of 5 mm. and atemperature of C. for 2 hours. The residue is boiled with water foronehalf hour and then neutralized with a dilute aqueous sodium hydroxidesolution. On evaporation of the water, 470 parts of sodium12-hydroxy-IZ-tricosanephosphonate is obtained. The sodium salt'is acontact insecticide, an effective dry-cleaning soap, and an effectivemold inhibitor. Dilute aqueous solutions of the sodium salt impart asoftened effect to viscose rayon. The free phosphonic acid isregenerated by treating the sodium salt with dilute hydrochloric acidand then extracting the mixture with petroleum ether. The petroleumether solution is then washed free of hydrochloric acid with a brinesolution. The free phosphonic acid is obtained by evaporation of thepetroleum ether. The free phosphonic acid, which has the consistency andcolor of honey, is an eflicient metal deactivator for motor fuels.

EXAMPLE III Disodium 2Jig drow-2-tridecanephosphonate A mixture of partsof tridecanone-2, 156 parts of phosphorus trichloride, and 137 parts ofglacial acetic acid is allowed to stand in the absence of moisture atroom temperature for 8 days. Volatile products are removed under vacuumon the steam bath and the residue boiled with water and subsequentlyneutralized with a dilute aqueous sodium hydroxide solution. The aqueoussolutions of this disodium 2-hydroxy-2-tridecanephosphonate foam readilyand display detergent action.

EXAMPLE IV Dipotassium 1 -:rylyl-1 -h'Jdromy-1 octadecanephosphonateFifteen parts of xylyl heptadecyl ketone, 13.7 parts of phosphorustrichloride, and 9 parts of glacial acetic acid are combined at roomtemperature and allowed to stand for 5 days with occasional agitation.The product is poured into 300 parts of water and' stirred rapidly atthe boiling point for one-half hour. The free acid thus producedseparates as large curds and is washed free of phosphate and chlorideions by decantation. The free acid is neutralized with a dilute aqueouspotassium hydroxideasolution. The potassium salt is an efiectivedry-cleaning soap and displays contact insecticidal action. Diluteaqueous solutions of the potassium salt foam readily, display detergentaction, and impart softening properties to viscose rayon.

By substituting biphenyl heptadecyl ketone and phenoxyphenylv heptadecylketone for the xylyl heptadecyl ketone in the preceding example,dipotassium i-biphenyl-l-hydroxy-l-octadec-anephosphonate anddipotassium 1 phenoxy Exmtn V Disodium hydroryphosphmiate derivative ofhydrogenated oiticica all To a mixture of 15 parts of hydrogenatedoiticica oil, 11 parts of phosphorus trichloride, and 11 parts ofglacial acetic acid sufiicient chloroform is added to give a homogeneoussolution. After standing for days with occasional agitation, the mixtureis-poured into boiling water and stirred until all the chloroform hasevaporated. The resulting acid is neutralized with a dilute aqueoussodium hydroxide solution. Dilute aqueous solutions of the sodium saltare effective softenlng agents for cotton textiles.

When oiticioa oil is treated in a similar fashion with phosphorustrichloride and the product hydrolyzed and neutralized with a. diluteaqueous sodium hydroxide solution, a water-soluble surface-activeproduct is obtained which is an effective textile softening agent.

EXAMPLEVI' Trisodium salt of lz hydroxydz-phosphonosteuric acid Amixture of 15 parts of lz-ketostearic acid, 11 parts of phosphorustrlchloride, and 13 parts of glacial acetic acid is combined in a.reaction vessel closed with a calcium chloride vent and suftl-= cientchloroform added to produce a homogeneous solution. After standing oneweek at room. temperature, the mixture is poured into 1000 parts ofwater, stirred, and boiled. The mixture is then evaporated to smallvolume, and the soft, wax-like phosphonic acid which separates is washedseveral times with warm water. drying, the free acid is dissolvedindilute ethanol and neutralized with a dilute aqueous sodium hydroxidesolution. The sodium saltisan'efiective mold inhibitor and is asoftening agent for viscose rayon. 1 I

When 12-ket0stearin is treated with phosphorus trichloride in a similarmanner and the resulting phosphonic acid converted to a sodium salt, asurface-active product is obtained which softens cotton fabrics.

In the process of the present invention, any ketone of at least tencarbon atoms wherein at least one and preferably both of the radicalsattached to the carbonyl carbon are completely open-chain aliphaticradicals may be reacted with any tervalent phosphorus compound where inat least one of the three phosphorus valences is attached to chlorine orbromine, i. e., to a halogen of atomicweight between 35 and 80, all thevalences of the phosphorus being attached to difierent atoms, i. e.,singly bonded.

In addition, therefore, to the ketones of the examples, the invention isapplicable to iii-ethyltetradecan-T-one; 2 methylhexadecan 5 one;pentadecan-9-one; 5 -ethyltetradecan-8-one; 7 methylpentadecan-Q-one; 2methylheptadecan- 4-one; 2 methyldodecan-4-one;2,8,12-trimethyltridecan-4-one; 2-methyl-8-ethyldodecan-5-one;5ethylhexadecan-8-one; 3-ethyltetradecan 6 one;3,9-diethyltridecan-6-one; 9-ethyltridecan- 6-one;6-propyl-8-ethyldodecan-5-one; 9-ethyl- 5-methyltridecan 6 one;pentadecan 8 one;

pentadecan-l-one; pentadecan-G-one; pentade can-5-one; pentadecani-one;pent'adecan 3 After all pentadecan-Z-one; Z-methyltetradecan 8-3-ethyltridecan-7-one; 4-propy1dodecan-6- one one;

one; 5-butylundecan-4-one; 6-amyldecan-3-one;

7-hexylnonan-2-one; 3-ethyltridecan-8-one; 4- prOPy1dodecan-7-one;S-butylundecan-fi-one; 6- amyldecani-one; 7-hexylnonan-3 one;5-butylundecan-ii-one; G-amyldecan 7 one; 7 hexylnonan-fi-one;tridecan-7-one; dodecan-G-one; 'lethyl-2-methylundecan-4-one;3-ethyldecan-fione; 3-ethylundecan-6-one; undecan-B-one; un-

decan--one; 5-ethylnonan-2-one; 2-methylundecan-S-one; heptadecan-S-one;heptadecanfi= one; heptadecan-B-one; heptadecan-7-one; heptadecan-5-one;heptadecanl-one; heptadecan- 3-one; S-ethylpentadecan-G-one;3-ethylpentadecan-4-one fi-ethylpentadecan-B-one 2,4,10,12-tetramethyltridencan-Z-one; 3-ethylpentadecan- 6-0218;2-methylhexadecan-5-one; 3,7-dimethylpentadecan-lO-one;nonadecan-lo-one; nonade can-Q-one; nonadecan-8-one; nonadecan-7-one;nonadecan fi-one; nonadecan-S-one; nonadecane-one; nonadecan-ii-one;nonadecan-z-one; 5,11 diethylpentadecan-B-one; 5-ethylheptadecan-8 one;5-ethylheptadecan-6-one; 2 methyloctadecan-5-one;2,6-dimethylheptadecanlo-one; 2,6- dimethyl-18-ethylpentadecan- 10 -one;2,6,10,14- tetramethylpentadecan- 8 -one; heneicosan 11 one;tricosan-lz-one; pentacosan-lIi-one; heptacosan-it-one;nonacosan-lS-one; hentriacontaniii-one; pentatriacontan-l8-one;dodec-ll-en-Z- one, etc. Itis frequently desirable to employ mixtures ofthe above ketones as starting materials for reaction with the phosphorushalides. A suitable mixture of ketones are those ketones obtained byketonizing the coconut oil acids which range in carbon content from 6 to18 carbon atoms. Other suitable ketones are the ketones which result bycondensing fatty acids with aromatic hydrocarbons, such as undecylphenyl ketone. tridecyl xylyl ketone, pentadecyl biphenyl ketone,heptadecyl naphthyl ketone, etc.

The invention is generic to the use of phosphorus trichloride andtri-bromide, monobromophosphines, monochlorophosphines,dibromophosphines and dichlorophosphines, includingbutyldichlorophosphine, phenyldichlorophos- *phine,dodecyldichlorophosphine, diphenylmonochlorophosphine,diamylmonochlorophosphine, dimethoxychlorophosphine, dibetanaphthyloxychlorophosphine, dicresyloxychlorophosphine,dioctyloxychlorophosphine, dicyclohexyloxychlorophosphine, monoethoxydichlorophosphine, mono-phenoxydichlorophosphine,monodecyloxydichlorophosphine, etc.

It is preferred to carry out the reaction between the ketones with theappropriate phosphorus halide in the presence of acetic acid or aceticanhydride, but any low molecular weight carboxylic acid or anhydride maybe used which does not react directly with the phosphorus halide usedunder the conditions of the reaction. Acetic anhydride is preferred whenthe intermediate phosphonyl chloride is desired, as is the case in thepreparation of the esters. It is recognized that the acid or anhydrideemployed as the medium in which the reaction takes place functions notonly as a solvent but is chemically involved in the reaction, probablyby reacting with a loose complex formed between the phosphorustrichloride or the chlorophosphine and the ketone. In this manner higheryields of the final product are obtained. However, the presence of suchan acid or anhydride is not essential, since low yields of tertiaryalphahydroxyphosphonic acid derivatives may be ob,-

preferred, however, tousemolecularly equivalent quantities of ketone andacetic anhydride, together with a slight excess of the phosphoroushalide. when acetic acid is employed. at least two molecular quantitiesare desirable. The reaction temperature may vary widely over aconsiderable range, the upper limitof which is chiefly determined by thetemperature at which the acid or anhydride employed begins to react withthe phosphorus trlchloride or the chlorophosphine directly. Thepreferred temperature for optimum results with acetic anhydride is therange of 20-50 C. when using benzoic acid, a higher temperature such as150 C. is sometimes desirable. Higher temperatures are sometimeseffective in'bringing about reaction with relatively inert ketones, butat the same time frequently result in a darkening and a slightresiniflcation of the reaction mixture. In general, the chlorophosphinesreact more slowly than the phosphorus trichloride and are'more expensiveintermediates than the phosphorus triehloride, and for these reasonsphosphorus trichloride is the preferred reagent. The esterificationreactions of the intermediate phosphonyl chlorides are. usually carriedout at temperatures of about 100 0., but higher temperatures may beemployed. When volatile reactants, such as methanol, etc., are used atthese elevated temperatures, it is usually desirable tocarry out thereaction in a closed vessel.

The phosphonic acids may be esterified with any non-acidic esterflableorganic hydroxyl compound, i. e., with alcohols and phenols includingmethanol, ethanol, isobutanol, hexan-l-ol, 2- ethylhexan-l-ol,dacan-l-ol, dodecan-l-ol, tetradecan-l-ol, hexadecan-l-ol,octadecan-l-ol, octadec-9-en-1-ol, pentadecan-S-ol, a mixture ofalcohols resulting from the catalytic hydrogenation or sodium reductionof natural oils such as coconut oil, sperm oil, eta; a mixture ofalcohols obtained in the catalytic synthesis of methanol from carbonoxides and hydrogen, cresols, naphthols, benzyl alcohoLcyclohexanol;naphthenyl alcohol, etc. The aliphatic alcohols are preferred to thearomatic phenolic compounds for the preparation of esters.

In many cases, it is not necessary to obtain the products of thisinvention in their pure state. In such cases, the procedure to befollowed consists merely in the water hydrolysis of the crude reactionmixture, followed if desired by neutralization of its acidity with anyalkaline agent. However, if pure products are desired, it is preferablefirst to remove the volatile reaction constituents such as aceticanhydride, acetic phenols,

aliphatic in nature.

to their alkali metal salts by neutralization with an alkali metalhydroxide such as sodium or potassium hydroinde, or ammonia; calcium and1 magnesium salts, and in fact any salt, may also be prepared and used.The soluble salts are. of course, of greatest utility. Salts of thephos-' phonic acids described herein may also be made from amines, e.g., dimethylamine, ethylamine,

diethanolamine, triethanolamine," butylamine,.

glucamine, methylglucamine, pyridine, piperidine, cyclohexylamine,aniline, toluidine, ethylenediamine, hexamethylenediamine, etc., andfrom quaternary ammonium bases, e. g., trlmethyl ammonium hydroxide.

The products of this invention are essentially In fact, in the preferredembodiment of the invention the products are entirely aliphatic innature and in general tend to be noncrystalline orlow melting incharacter, thereby enhancing their compatibility characteristics withaliphatic hydrocarbons of the motor fuel and lubricant types. Thepredominantly aliphatic properties of the higher molecular weightcompounds containing a water solubilizing phos-- phonate group'rendersthem similar to the soaps of the higher molecular weight fatty acidswhich are dependent uponan aliphatic lipophile radical for theircapillary active characteristics.

The t e r ti a r y alpha-hydroxyphosphonates which are derived fromketones are preferred to the non-tertiary alpha-hydroxyphosphonateswhich are derived from aldehydes because of -the greater availabilityand stability of the ketones.

The products of thisinvention preferably those of twelve or more carbonatoms, which by reason of a free acid group or its equivalent salt, are

soluble in water, belong to the class of surfaceactive or capillaryactive materials in that they have colloidal properties and maytherefore be used advantageously in any process involving wetting,penetrating, deterging, dispersing, emulsifying, frothing, foaming, oreflotation and kindred phenomena. Since the high. molecular weightproducts of this invention have surfacetension lowering properties, theymay be utilized in many of the technical applications of surface- Aactive compounds. The products of this invenacid, acyl chloride,unchanged phosphorus trition have special value as detergents andwetting agents, as dry-cleaning soaps, as mold inhibitors, and astextile softening agents.

The acids and esters of this new class of organic phosphorus derivativeshave a varied and beneficial action as lubricant addition agents andmodifying agents for motor fuel, for example, as metal deactivators andthe like. The action of phosphonic acids as metal deactivators in motorfuels is disclosed in copending application Serial Number 302,856, filedNovember 4, 1939, by Elmer K. Bolton.

The above description and examples are intended to be illustrative only.Any modification of or variation therefrom which conforms to the spiritof the invention is intended to be included within the scope of theclaims.

We claim:

1. An organic compound of quinquevalent phosphorus wherein one valenceof the phosphorus is attached to an organic radical containing noelements other than carbon, hydrogen and oxygen and having at least tencarbon atoms through a carbon atom which is also attached to a hydroxylgroup and to two other carbons at least one of which forms part of anopen-chain aliphatic radical, two other valences of the phosphorus beingattached to one oxygen atom.

2. Tertiary alpha-hydroxyphosphonates or the formula \P-G tn wherein theradicals R are organic radicals containing no elements other thancarbon, hydrogen and oxygen, RCR contains at least ten carbon atoms, atleast one or the organic radicals R is an aliphatic radical, G is amember of the class consisting of OH, OM, R, and OR, and M is a cationof the class consisting of hydrogen and salt-forming atoms and groups.

3. An organic compound oi quinquevalent phosphorus wherein one valenceof the phosphorus is attached to an organic radical containing noelements other than carbon, hydrogen and oxygen and having at least tencarbon atoms through a carbon atom which is also attached to a hydroxygroup and to two other carbons at least phatic radical attached to thecarbonyl comone of which forms part of an open-chain aliphatic radical,two other valences of the phosphorus being attached to one oxygen atom,the remaining valences oi the phosphorus being satisfied by hydroxylgroups.

4. A salt of a compound according to claim 3.

5. A water-soluble salt of a compound according to claim 3.

6. An alkali-metal water-soluble salt of a compound according to claim3.

'7. A sodium salt of a compound according to claim 3.

8. Process which comprises reacting a ketone of at least ten carbonatoms having at least one open-chain aliphatic radical attached to thecarbonyl group with a bromide or chloride of tervalent phosphorus, allvalences of which are satisfied by single bonds, preferably in thepresence of a low molecular weight organic monocarboxylic acid oranhydride.

9. Process which comprises reacting phosphorus trichloride with a ketoneof at least ten carbon atoms having at least one open-chain aliphaticradical attached to the carbonyl compound in the presence or a lowmolecular weight organic monocarboxylic acid.

10. Process which comprises reacting phosphorus trichloride with aketone or at least ten carbon atoms having at least one open-chainaliphatic radical attached to the carbonyl compound in the presence ofacetic anhydride.

11. Process which comprises reacting a ketone of at least ten carbonatoms having at least one open-chain aliphatic radical attached to thecarbonyl group with a bromide or chloride of tervalent phosphorus, allvalences or which are satisfied by single bonds, preferably in thepresence of a low molecular weight organic mono carboxylic acid oranhydride, and treating the resulting product with water.

12. Process which comprises reacting a ketone oi at least ten carbonatoms having at least one open-chain aliphatic radical attached to. thecarbonyl group with a bromide or chlorid of tervalent phosphorus, allvalences of which are satisfied by single bonds, preferably inthepresence of a low molecular weight organic monocarboxylic acid oranhydride, and treating the resulting product with water containing analkali metal hydroxide.

13. Process which comprises reacting phosphorus trichloride with aketone'oi at least ten pound in the presence of a low molecular weightorganic monocarboxylic aid, and treating the resulting product withaqueous alkali.

14. An organic compound or quinquevalent phosphorus wherein one valenceof the phosphorus is attached to an organic radical oi! at least tencarbon atoms through a carbon atom which is also attached to a hydroxylgroup and to two other carbons each or which forms part of a completelyopen-chain aliphatic radical, two other valences of the phosphorus beingattached -to one oxygen atom.

15. Tertiary alpha-hydroxyphosphonates of the formula 0% P-G tn whereinRC-R contains at least ten carbon atoms, each or the organic radicals Ris an aliphatic radical, G is a member or the class consisting of OH,OM, R and OR, and M is a cation of the class consisting of hydrogen andsalt-forming atoms and groups,

16. An organic compound of quinquevalent phosphorus wherein one valenceof the phosphorus is attached to an organic radical of at least tencarbon atoms through a carbon atom which is also attached to a hydroxylgroup and to two other carbons each of which forms part or an open-chainaliphatic radical, two other valences oi the phosphorus being attachedto one oxygen atom, the remaining valences oi. the phosphorus beingsatisfied by hydroxyl groups.

17. A salt of the compound according to claim 16.

18. An alkali metal salt of a compound according to claim 16.

19. A sodium salt of a compound according to claim 16.

20. An organic compound of quinquevalent phosphorus wherein one valenceof the phosphorus is attached to a hydrocarbon radical of at least tencarbon atoms through a carbon atom which is also attached to a hydroxylgroup and to two other carbons at least one of which forms part of anopen-chain aliphatic radical, two other valences of the phosphorus beingattached to one oxygen atom.

21. Tertiary alpha hydroxyphosphonates of the formula wherein R-CRcontains at least ten carbon atoms, at least one or the hydrocarbonradicals R is an aliphatic radical, G is a member 0! the classconsisting of OH, OM, R and OR, and M is a cation of the classconsisting of hydrogen and salt-forming atoms and groups.

22. An organic compound of quinquevalent phosphorus wherein one valenceof the phosphorus is attached to a hydrocarbon radical of at least tencarbon atoms through a carbon atom which is also attached to a hydroxylgroup and to two other carbons at least one of which forms part 01' anopen-chain aliphatic radical, two other valences or the phosphorus beingattached to one oxygen atom, the remaining valences of the phosphorusbeing satisfied by hydroxyl groups.

23. A salt of a compound according to claim 22.

24. A water-soluble salt of a compound according to claim 22.

25. A'aodlum salt of a compound according to 29. A- derivative ofoiticlca 011 wherein tho kcto 511111133- mens of the oiticica oil arceach replaced by 28. An alkali-metal water-aoluble salt of a onehydroxyl group and one NazOaP-aroup. compound according to claim 22.

27. Dlaodlum 8-hydroxy- 8 -pentadecanephoa- 5 PHEIP. GREELEY STEVENS.phonate. HOWARD SINCLAIR TURNER.

28. Dipotassium l-xylyl-l hydroxy 1 octadccanephosphonatc.

CERTIFICATE or conmsc'non. Patent no, 2,25h,12h. August 26, 19!;1.

PHILIP GREELE! STEVENS, ET AL.

It is herehy certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Pagel,first column, line 114-15, ior"imparts" read' --impart--; page 5,secondcolumn, line 17, for "tetramethyltridencan" read--tetramethy'ltridecan--; {page 1; first column, line 12, for "ketone"read---ketones--; line. for -"dacan-l-ol" read --decan-l-ol--; page 5,first column, line 22-25, claim 5, for "hydroxy" read hydroxyl-; andsecond column, line D claim 15,

for the word "aid" read -acid--; and that the said Letters Patent shouldbe read with this correction therein that the game may confonn'to therecord of the case in the Patent Office.

Signed and sealed this 18th day of November, A. D. 19in.

Henry Van Arsdale,

(Seal) Acting Comnissioner of Patents.

